270 Organometallics, Vol. 21, No. 2, 2002
Meijer et al.
(Ar-C), 137.38 (d, 1J (P-C) ) 6.1 Hz, PAr-Cipso), 135.18 (d,
2J (P-C) ) 11.0 Hz, Ar-Cortho), 131.61 (d, 2J (P-C) ) 2.5 Hz,
136.22 (d, 2J (P-C) ) 2.4 Hz, Ar-C), 135.13 (d, 4J (P-C) ) 11.0
1
Hz, PAr-Cortho), 136.64 (d, J (P-C) ) 6.7 Hz, PAr-Cipso), 132.4
4
Ar-C), 130.64 (Ar-C), 130.53 (d, J (P-C) ) 2.4 Hz, PAr-Cpara),
(3J (Pt-C) ) 29.0 Hz, Ar-C), 131.67 (3J (Pt-C) ) 30.4 Hz, Ar-
C), 130.34 (PAr-Cpara), 127.69 (d, 3J (P-C) ) 10.9 Hz, PAr-
3
129.82, 127.81 (d, J (P-C) ) 11.0 Hz, PAr-Cmeta), 122.91 (Ar-
C), 121.56 (Ar-C), 74.0 (2J (Pt-C) ) 56.3 Hz, CH2N), 67.2
(OCH2), 61.4 (OEt), 50.8 (NCH3), 41.3 (C(O)CH2C(O)), 14.0
(OEt). 31P{1H} NMR (CDCl3): δ 21.2 (1J (Pt-P) ) 4236 Hz).
Anal. Calcd for C33H35ClNO4PPt: C 51.40, H 4.57, N 1.82.
Found: C 51.24, H 4.65, N 1.74.
C
meta), 121.85 (Ar-C), 121.14 (Ar-C), 74.1 (2J (Pt-C) ) 46.7 Hz,
CH2N), 61.1 (OEt), 53.3, 52.9 (NCH3), 40.9 (C(O)CH2C(O)), 14.0
(OEt). 31P{1H} NMR (CDCl3): δ 20.0 (1J (Pt-P) ) 4202 Hz).
Anal. Calcd for C60H60I2N2O4P2Pt2: C 45.64, H 3.83, N 1.77.
Found: C 45.88, H 3.76, N 1.85.
1-{Bis(3′-[ch lor o(t r ip h en ylp osp h in e)p la t in o]-4′-[(d i-
m et h yla m in o)m et h yl]p h en yl)m et h yl}-3-et h ylm a lon a t e
(11). Compound 11 was prepared using the same method as
for 10 starting from 6 (2.28 g, 1.78 mmol), ethyl malonyl
chloride (0.34 mL, 2.7 mmol), and NEt3 (0.37 mL, 2.7 mmol),
1,2-Dih ydr o-61-eth oxycar bon yl-61-{4-[(dim eth ylam in o)-
m et h yl]b en zyloxyca r b on yl}-1,2-m et h a n o[60]fu ller en e
(14). To a solution of 8 (0.38 g, 1.3 mmol), C60 (0.91 g, 1.3
mmol), and I2 (0.65 g, 2.5 mmol) in toluene (900 mL) was added
dropwise DBU (1.1 mL, 7.1 mmol). The reaction mixture was
stirred for 17 h and poured on top of a silica gel column.
Elution with toluene afforded 0.20 g of unreacted C60. Elution
with toluene/MeOH (95:5 v/v %) gave the crude product after
evaporation of the solvent. This was dissolved in CS2 (10 mL)
and pentane was added (75 mL), whereupon the product
precipitated. This procedure was repeated and the precipitate
dried in vacuo, yielding 14 as a light brown solid (0.44 g, 35%,
1
yielding 11 as a white solid (1.90 g, 76%). H NMR (CDCl3):
δ 7.71-7.65 (m, 12H, PAr-H), 7.43-7.26 (m, 18H, PAr-H), 6.67
3
(d, J ) 7.5 Hz, 2H, Ar-H), 6.39 (3J (Pt-H) ) 55.2 Hz, 2H, Ar-
3
4
H
ortho), 5.79 (dd, J ) 7.8 Hz, J ) 0.9 Hz, 2H, Ar-H), 5.47 (s,
3
1H, OCH), 4.08 (q, 2H, J ) 6.9 Hz, OEt), 4.01/3.95 (dd, AB,
3J ) 13.5 Hz, 3J (P-H) ) 2.7 Hz, 4H, CH2N), 2.96, 2.93 (2 × d,
3J (P-H) ) 2.7 Hz, 12H, NCH3), 2.46 (s, 2H, C(O)CH2C(O)),
1.15 (t, 3J ) 6.9 Hz, OEt). 13C{1H} NMR (CDCl3): δ 146.47
(Ar-C), 136.64 (d, 1J (P-C) ) 6.7 Hz, PAr-Cipso), 136.47 (d,
1
45% based on reacted C60). H NMR (CS2/C6D6, 3:1 v/v %): δ
3
3
7.23 (d, J ) 8.4 Hz, 2H, Ar-H), 7.21 (d, J ) 8.4 Hz, 2H, Ar-
H), 5.25 (s, 2H, OCH2), 4.21 (q, 3J ) 7.2 Hz, 2H, OEt), 3.27 (s,
2H, CH2N), 2.09 (s, 6H, NCH3), 1.14 (t, 3J ) 7.2 Hz, 3H, OEt).
13C{1H} NMR (CS2/C6D6, 3:1 v/v %): δ 162.73, 162.64 (CO),
144.63, 145.48, 145.46, 145.38, 145.07, 144.96, 144.91, 144.87,
144.82, 144.14, 143.31, 143.25, 142.48, 142.09, 141.19, 141.17,
140.62, 139.56, 139.38, 133.67, 129.24, 129.17 (C60-C and Ar-
C), 71.9 (C60-sp3), 68.6, (OCH2), 64.2 (CH2N), 63.2 (OEt), 52.2
(C(O)CH2C(O)), 45.6 (NCH3), 14.4 (OEt). MALDI-TOF (9-
NA): m/z 997.0 ([M]+). Anal. Calcd for C75H19NO4: C 90.26,
H 1.92, N 1.40. Found: C 90.05, H 1.86, N 1.32.
2J (P-C) ) 2.4 Hz, Ar-C), 135.12 (d, J (P-C) ) 10.9 Hz, PAr-
4
C
ortho), 130.8 (Ar-C), 130.46 (d, 4J (P-C) ) 1.8 Hz, Ar-Cpara),
130.03 (Ar-C), 127.80 (d, 3J (P-C) ) 11.6 Hz, PAr-Cmeta), 121.63
(Ar-C), 121.29 (Ar-C), 77.8 (OCH), 74.1 (2J (Pt-C) ) 49.7 Hz,
CH2N), 61.1 (OEt), 50.9, 50.8 (NCH3), 40.8 (C(O)CH2C(O)), 14.0
(OEt). 31P{1H} NMR (CDCl3): δ 21.6 (1J (Pt-P) ) 4262 Hz).
Anal. Calcd for C60H60Cl2N2O4P2Pt2: C 51.62, H 4.33, N 2.01.
Found: C 51.69, H 4.28, N 1.97.
1-{4′-[(Dim eth yla m in o)m eth yl]-3′-[iod o(tr ip h en ylp os-
p h in e)p la tin o]ben zyl}-3-eth ylm a lon a te (12). To a solution
of 10 (0.44 g, 0.57 mmol) in acetone (25 mL) was added NaI
(0.85 g, 4.4 mmol). The reaction mixture was stirred for 2 h
and evaporated in vacuo. The resultant white solid was
extracted with CH2Cl2 (20 mL). Hexanes (60 mL) were added
to the solution, whereupon a precipitate was formed. This was
isolated and dried in vacuo, giving 12 as a tan solid (0.40 g,
1,2-Dih yd r o-61-et h oxyca r b on yl-61-{b is{4′-[(d im et h -
y la m i n o )m e t h y l]p h e n y l}m e t h y lo x y c a r b o n y l}-1,2-
m eth a n o[60]fu ller en e (15). To a solution of 9 (0.41 g, 0.99
mmol), C60 (0.86 g, 1.2 mmol), and I2 (0.51 g, 2.0 mmol) in
toluene (900 mL) was added DBU (0.90 mL, 7.0 mmol)
dropwise. The reaction mixture was stirred for 17 h and poured
on top of a silica gel column. Elution with toluene afforded
0.23 g of unreacted C60. Elution with toluene/MeOH (95:5 v/v
%) gave the crude product after evaporation of the solvent.
This was dissolved in CS2 (10 mL), and acetone was added
(75 mL), whereupon the product precipitated. This was
isolated, washed with acetone (40 mL), and dried in vacuo,
yielding 15 as a light brown solid (0.53 g, 47%, 54% based on
reacted C60). 1H NMR (CDCl3): δ 7.41 (d, 3J ) 8.1 Hz, 4H,
Ar-H), 7.31 (d, 3J ) 8.1 Hz, 4H, Ar-H), 7.26 (s, 1H, OCH), 4.51
(q, 3J ) 7.5 Hz, 2H, OEt), 3.41 (s, 4H, CH2N), 2.23 (s, 12H,
1
81%). H NMR (CDCl3): δ 7.77-7.69 (m, 6H, PAr-H), 7.44-
7.31 (m, 9H, PAr-H), 7.02 (d, 3J ) 7.5 Hz, 1H, Ar-H), 6.86 (dd,
3J ) 7.8 Hz, 4J ) 1.8 Hz, 1H, Ar-H), 6.35 (dd, 3J (Pt-H) )
4
4
58.2 Hz, J (P-H) ) 3.6 Hz, J ) 1.5 Hz, 1H, Ar-Hortho), 4.48
3
3
(s, 2H, OCH2), 4.17 (q, 2H, J ) 6.9 Hz), 4.09 (d, J (Pt-H) )
3
3
24.0 Hz, J (P-H) ) 2.4 Hz, 2H, CH2N), 3.15 (d, J (Pt-H) )
24.6 Hz, 3J (P-H) ) 3.0 Hz, 6H, NCH3), 3.12 (s, 2H, C(O)CH2C-
(O)), 1.23 (t, 3J ) 6.9 Hz, OEt). 13C{1H} NMR (CDCl3): δ 147.64
(Ar-C), 136.35 (d, 1J (P-C) ) 6.7 Hz, PAr-Cipso), 135.31 (d,
2J (P-C) ) 10.4 Hz, Ar-Cortho), 132.28 (Ar-C), 131.62 (d, 4J (P-
C) ) 2.5 Hz, Ar-C), 130.46 (Ar-C), 130.60 (d, 4J (P-C) ) 3.3
Hz, Ar-Cpara), 127.76 (d, 3J (P-C) ) 11.5 Hz, PAr-Cmeta), 123.14
(Ar-C), 121.80 (3J (Pt-C) ) 32.8 Hz, Ar-C), 74.2 (2J (Pt-C) )
53.4 Hz, CH2N), 67.2 (OCH2), 61.5 (OEt), 53.2 (NCH3), 41.4
(C(O)CH2C(O)), 14.1 (OEt). 31P{1H} NMR (CDCl3): δ 19.7
3
NCH3), 1.14 (t, J ) 7.2 Hz, 3H, OEt). 13C{1H} NMR (CDCl3):
δ 163.51, 162.72 (CO), 145.30, 145.26, 145.20, 145.17, 145.15,
145.03, 144.91, 144.91, 144.88, 144.71, 144.69, 144.67, 144.63,
144.46, 143.89, 143.83, 143.06, 143.01, 142.98, 142.97, 142.22,
142.21, 140.94, 142.21, 141.86, 140.94, 140.90, 139.63, 139.36,
138.51, 137.61, 129.16, 127.62 (C60-C and Ar-C), 79.7 (OCH),
71.5 (C60-sp3), 64.0 (CH2N), 63.5 (OEt), 52.1 (C(O)CH2C(O)),
45.5 (NCH3), 14.2 (OEt). MALDI-TOF (9-NA): m/z 1131.5
([M]+). Anal. Calcd for C84H30N2O4: C 89.19, H 2.67, N 2.48.
Found: C 89.28, H 2.57, N 2.50.
(1J (Pt-P) ) 4189 Hz). Anal. Calcd for C33H35INO4PPt:
45.95, H 4.09, N 1.62. Found: C 45.80, H 3.98, N 1.58.
C
1-{Bis(4′-[(d im et h yla m in o)m et h yl]-3′-[iod o(t r ip h en -
ylposph in e)platin o]ph en yl)m eth yl}-3-eth ylm alon ate (13).
To a solution of 11 (1.43 g, 1.02 mmol) in acetone (50 mL) was
added NaI (1.5 g, 10 mmol). The reaction mixture was stirred
for 2 h and evaporated in vacuo, and the remaining solid was
extracted with CH2Cl2 (50 mL). This was evaporated in vacuo,
1,2-Dih yd r o-61-eth oxyca r bon yl-61-{3′-[ch lor o(DMSO)-
platin o]-4′-[(dim eth ylam in o)m eth yl]ben zyloxycar bon yl}-
1,2-m eth a n o[60]fu ller en e (16). To a solution of 14 (227 mg,
0.227 mmol) in 1,2-dichlorobenzene (50 mL) was added cis-
PtCl2(DMSO)2 (101 mg, 0.239 mmol) and a solution of NaOAc
(20 mg, 0.24 mmol) in MeOH (20 mL). The reaction mixture
was heated at 65 °C for 17 h and evaporated in vacuo. The
crude product was extracted with CS2 (40 mL), filtered, and
evaporated in vacuo. The product was washed with MeOH (2
× 40 mL) and Et2O (2 × 40 mL) and dried in vacuo, yielding
1
yielding 13 as a tan solid (1.38 g, 86%). H NMR (CDCl3): δ
7.72-7.63 (m, 12H, PAr-H), 7.38-7.27 (m, 18H, PAr-H), 6.68
(d, 3J ) 7.8 Hz, 2H, Ar-H), 6.39 (dd, 3J (Pt-H) ) 59.8 Hz, 4J (P-
H) ) 3.5 Hz, 4J ) 1.2 Hz, 2H, Ar-Hortho), 5.70 (dd, 3J ) 7.6 Hz,
3
4J ) 1.2 Hz, 2H, Ar-H), 5.52 (s, 1H, OCH), 4.08 (q, 2H, J )
3
3
7.5 Hz, OEt), 4.05/3.99 (dd, AB, J ) 13.4 Hz, J (P-H) ) 3.0
Hz, 4H, CH2N), 3.15, 3.09 (2 × d, 3J (P-H) ) 2.7 Hz, 12H,
3
1
NCH3), 2.52 (s, 2H, C(O)CH2C(O)), 1.15 (t, J ) 6.9 Hz, OEt).
16 as a brown solid (168 mg, 57%). H NMR (CDCl3): δ 8.10
13C{1H} NMR (CDCl3): δ 166.04, 164.43 (CO), 146.45 (Ar-C),
(d, J (Pt-H) ) 45.9 Hz, J ) 1.2 Hz, 1H, Ar-Hortho), 7.26 (dd,
3
4